Field effect transistor and method of manufacturing the same

ABSTRACT

Provided is a field effect transistor having an organic semiconductor layer, in which the organic semiconductor layer contains at least a tetrabenzo copper porphyrin crystal and has peaks at two or more of Bragg angles (2θ) in CuKα X-ray diffraction of 8.4°±0.2°, 10.2°±0.2°, 11.80°±0.20°, and 16.90°±0.20°, and the tetrabenzo copper porphyrin crystal comprises a compound represented by the following general formula (1): (Wherein R 2 &#39;s each represent a hydrogen atom, a halogen atom, a hydroxyl group, or an alkyl group, oxyalkyl group, thioalkyl group, or alkylester group having 1 to 12 carbon atoms, and R 3 &#39;s each represent a hydrogen atom or an aryl group.)

TECHNICAL FIELD

The present invention relates to a field effect transistor having anorganic semiconductor layer using a tetrabenzo copper porphyrin crystaland a method of manufacturing the field effect transistor.

BACKGROUND ART

The nonlinear optical characteristics, conductivity, andsemiconductivity of an organic semiconductor compound have attractedattention in the field of optoelectronics, so that the development ofvarious devices has been vigorously conducted.

In recent years, a field effect transistor (FET) element using anorganic semiconductor compound for its semiconductor layer has beenattracting attention. In view of this circumstance, an organicsemiconductor compound is now considered to be suitable for thepreparation of a flexible element using plastics as its substratebecause the organic semiconductor compound exhibits flexible filmproperty as compared to an inorganic material such as silicon.

Representative examples of such an organic semiconductor compoundinclude phthalocyanine-based compounds and polyacenes. Characteristicssuch as nonlinear optical characteristics, conductivity, andsemiconductivity necessary for preparing devices using those compoundsas organic materials are known to largely depend on the crystallinityand orientation of the materials as well as their purities. However, ithas been difficult to make many compounds such as thephthalocyanine-based compound and the polyacenes mentioned earlier, inwhich π conjugated systems are extended, highly pure partly because thecompounds are insoluble in solvents and susceptible to oxidation in theatmosphere. Moreover, a large-scale apparatus has been necessary forfilm formation partly because vacuum evaporation should be performed inorder to obtain a crystallized film having high orientation.

For instance, pentacene, a representative example of an organicsemiconductor compound, can be formed into a film on a substrate bymeans of vacuum evacuation alone because pentacene has highcrystallinity and is insoluble in a solvent.

Meanwhile, a FET is prepared more simply by forming a thin film using asolution of an organic semiconductor that is soluble in an organicsolvent by means of a coating method such as a spin coating method.Examples of such a FET include one using a π-conjugated polymer for itssemiconductor layer (see “Japanese Journal of Applied Physics”, JapanSociety of Applied Physics, vol. 30, pp. 596-598, 1991). It is knownthat, in the case of a π-conjugated polymer, an arrangement state ofmolecular chains largely affect electric conductive characteristics.Similarly, it has been reported that a field effect mobility of aπ-conjugated polymer field effect transistor is largely dependent on thearrangement state of the molecular chains in the semiconductor layer(see “Nature”, Nature Publishing Group, vol. 401, pp. 685-687, 1999).

However, the arrangement of the molecular chains of a π-conjugatedpolymer is performed during a period from solution coating to solutiondrying. Therefore, there is a possibility that the arrangement state ofthe molecular chains varies to a large extent owing to an environmentalchange or depending on coating method. In view of this, there has beenreported a FET using a film obtained by: forming a thin film of asoluble precursor of pentacene through coating; and subjecting the thinfilm to heat treatment to transform the precursor into pentacene (see“Advanced Materials”, WILLEY-VCH Verlag GmbH, vol. 11, pp. 480-483,1999). In this case, the transformation into pentacene necessitateshigh-temperature treatment, and an eliminated component having a largemass must be removed under reduced pressure.

As described above, a conventional FET element using an organicsemiconductor compound has required a complicated step such as vacuumfilm formation, or involved a problem in that the element is easilyaffected by the environment.

DISCLOSURE OF THE INVENTION

The present invention has been made in order to solve the aboveproblems, and therefore an object of the present invention is to providea field effect transistor which can be manufactured by a method muchsimpler than a conventional method and which exhibits a high fieldeffect mobility, and to provide a method of manufacturing the fieldeffect transistor.

That is, according to one aspect of the present invention, there isprovided a field effect transistor having an organic semiconductorlayer, in which the organic semiconductor layer contains at least atetrabenzo copper porphyrin crystal and has peaks at two or more ofBragg angles (2θ) in CuKα X-ray diffraction of 8.40°±0.2°, 10.20°±0.2°,11.80°±0.2°, and 16.90°±0.20.

In further aspect of the field effect transistor, the tetrabenzo copperporphyrin crystal comprises a compound represented by the followinggeneral formula (1).

(Wherein R₂'s each independently represent at least one kind selectedfrom the group consisting of a hydrogen atom, a halogen atom, a hydroxylgroup, and an alkyl group, oxyalkyl group, thioalkyl group, oralkylester group having 1 to 12 carbon atoms, and R₃'s represent atleast one kind selected from the group consisting of a hydrogen atom andan aryl group.)

In further aspect of the field effect transistor, the tetrabenzo copperporphyrin crystal is obtained by heating a compound represented by thefollowing general formula (2).

(Wherein R₁'s and R₂'s each independently represent at least one kindselected from the group consisting of a hydrogen atom, a halogen atom, ahydroxyl group, and an alkyl group, oxyalkyl group, thioalkyl group, oralkylester group having 1 to 12 carbon atoms, and R₃'s represent atleast one kind selected from the group consisting of a hydrogen atom andan aryl group.)

In the compound represented by the general formula (2), 8 kinds ofisomers can be present depending on whether a double bond of a bicycloring is present above or below a porphyrin ring plane. However, a mixingratio of the isomers is arbitrary.

According to another aspect of the present invention, there is provideda method of manufacturing a field effect transistor having an organicsemiconductor layer, including the step of forming the organicsemiconductor layer containing at least a tetrabenzo copper porphyrincrystal and having peaks at two or more of Bragg angles (2θ) in CuKαX-ray diffraction of 8.4°±0.20°, 10.20°±0.20, 11.80°±0.20°, and16.90°±0.20°, in which the step of forming the organic semiconductorlayer is performed by heating a thin film comprising a compoundrepresented by the general formula (2) to produce the tetrabenzo copperporphyrin crystal.

According to the present invention, there can be provided a field effecttransistor exhibiting a high field effect mobility.

In addition, according to the present invention, there can be provided amethod of manufacturing a field effect transistor exhibiting a highfield effect mobility, with which an organic semiconductor layer can beformed much simply than a conventional method.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an X-ray diffraction pattern of a transistor substrateobtained in Example 1 of the present invention;

FIG. 2 is an X-ray diffraction pattern of a quartz substrate obtained inExample 1 of the present invention;

FIG. 3 shows electrical characteristics of a field effect transistor inExample 1 of the present invention;

FIG. 4 is an enlarged schematic diagram of a part of a field effecttransistor of the present invention; and

FIG. 5 is an enlarged schematic diagram of a part of a field effecttransistor of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, an embodiment of the present invention will be described indetail.

A field effect transistor of the present invention is characterized inthat an organic semiconductor layer is used, which contains at least atetrabenzo copper porphyrin crystal and has peaks at two or more ofBragg angles (2θ) in CuKα X-ray diffraction of 8.4°±0.2°, 10.20°±0.20°,11.8°±0.20°, and 16.90°±0.20°.

The tetrabenzo copper porphyrin crystal has a structure represented bythe following general formula (1) and can be obtained by heating acompound represented by the following general formula (2).

(Wherein R₂'s each independently represent at least one kind selectedfrom the group consisting of a hydrogen atom, a halogen atom, a hydroxylgroup, and an alkyl group, oxyalkyl group, thioalkyl group, oralkylester group having 1 to 12 carbon atoms, and R₃'s represent atleast one kind selected from the group consisting of a hydrogen atom andan aryl group.)

(Wherein R₁'s and R₂'s each independently represent at least one kindselected from the group consisting of a hydrogen atom, a halogen atom, ahydroxyl group, and an alkyl group, oxyalkyl group, thioalkyl group, oralkylester group having 1 to 12 carbon atoms, and R₃'s represent atleast one kind selected from the group consisting of a hydrogen atom andan aryl group.)

In the compound represented by the general formula (2), 8 kinds ofisomers can be present depending on whether a double bond of a bicycloring is present above or below a porphyrin ring plane. However, a mixingratio of the isomers is arbitrary.

The field effect transistor using an organic semiconductor layer, thesemiconductor layer containing at least a tetrabenzo copper porphyrincrystal and having peaks at two or more of Bragg angles (2θ) in CuKαX-ray diffraction of 8.4°±0.2°, 10.20°±0.20°, 11.80°±0.20°, and16.90°±0.2°, can be manufactured by a method much simpler than aconventional method and exhibits a high mobility.

The X-ray diffraction measurement of the present invention was performedby using a CuKα ray under the following conditions.

-   Sample: prepared by forming a thin film containing a tetrabenzo    copper porphyrin crystal into a substrate by a method described in    Examples-   Machine used: RAD-RX wide angle X-ray diffraction instrument    manufactured by Rigaku Corporation-   X-ray tube: Cu-   Tube voltage: 50 kV-   Tube current: 150 mA-   Scanning method: 2θ/θ scan-   Sampling interval: 0.02 deg.-   Integrating time: 1 s-   Number of times of integration: 14 times-   Measurement temperature: room temperature (20° C.)

The present invention will be described in more detail.

In the present invention, substituents R₁'s bound to bicyclooctaenerings of a bicycloporphyrin compound represented by the general formula(2) (hereinafter, referred to as bicyclo compound) are eliminated asR₁—CH═CH—R₁ when the compound is transformed into a tetrabenzo porphyrincompound represented by the general formula (1) (hereinafter, referredto as benzo compound) through heat treatment. Therefore, R₁'s have onlyto be each independently at least one kind selected from the groupconsisting of a hydrogen atom, a halogen atom, a hydroxyl group, and analkyl group, oxyalkyl group, thioalkyl group, or alkylester group having1 to 12 carbon atoms, and two or more kinds of them may be combined. Ifthe number of carbon atoms exceeds 12, an eliminated component has anincreased molecular weight, so that the eliminated component remains ina benzo compound film, thereby making it impossible to obtain sufficientsemiconductor characteristics. R₁'s are most preferably hydrogen atoms.

Substituents R₂'s of the bicyclo compound represented by the generalformula (2) remain as substituents even in the benzo compoundrepresented by the general formula (1) obtained after the heattreatment. Therefore, the substituents R₂'s affect the orientation ofthe benzo compound. R₂'s have only to be each independently at least onekind selected from the group consisting of a hydrogen atom, a halogenatom, a hydroxyl group, and an alkyl group, oxyalkyl group, thioalkylgroup, or alkylester group having 1 to 12 carbon atoms, and two or morekinds of them may be combined. If the number of carbon atoms in an R₂exceeds 12, an existence of a porphyrin ring with respect to the entiremolecule lowers, so that the porphyrin rings are hardly oriented,thereby making it impossible to obtain sufficient semiconductorcharacteristics. R₂'s are most preferably hydrogen atoms. In this case,the stacking of the porphyrin rings occurs more easily, so that filmcrystallinity increases.

A preferable method of preparing an organic semiconductor layerinvolves: dissolving a bicyclo compound into an organic solvent; coatinga substrate with the solution; and heating the solution to obtain acrystallized film of a benzo compound.

An organic solvent used for dissolving a bicyclo compound is notparticularly limited as long as the bicyclo compound does not react withthe organic solvent and the bicyclo compound is not precipitated in theorganic solvent. In addition, two or more kinds of organic solvents maybe mixed when in use. A halogen solvent is preferably used in view ofsmoothness of a coating film surface and uniformity of the filmthickness. Examples of a halogen solvent include chloroform, methylenechloride, dichloroethane, chlorobenzene, and 1,2-dichloroethylene. Theconcentration of the solution, which is arbitrarily adjusted dependingon a desired film thickness, is preferably 0.01 to 5 wt %.

Examples of a coating method include a spin coating method, a dippingmethod, a dropping method, an offset, screen, and other printingmethods, and an ink jet method. In addition, it is desirable to filterthe solution through a membrane filter in advance in order to minimizethe mixing of foreign material or the like into a semiconductor layer.This is because the mixing of insoluble matter or foreign material fromthe outside prevents uniform orientation, thereby causing an increase inoff-state current or a reduction in on/off ratio. In addition, thecoating film of the bicyclo compound can be predried at a temperatureequal to or lower than 130° C.

The coated and formed film of the bicyclo compound is heated to cause aretro Diels-Alder reaction, thereby undergoing a transformation into abenzo compound involving the elimination of R₁-CH═CH—R₁. Crystal growthdue to the stacking of the porphyrin rings occurs simultaneously withthe formation of the benzo compound, and hence a crystallized film ofthe benzo compound can be obtained. In addition, an elimination reactionoccurs at a temperature equal to or higher than 150° C. A heatingtemperature for obtaining a higher field effect mobility is desirably inthe range of 170 to 280° C., preferably 200 to 230° C. A heatingtemperature of lower than 170° C. cannot provide a crystallized filmhaving undergone sufficient crystal growth whereas a heating temperaturein excess of 280° C. develops a crack owing to abrupt film contraction.

The heating of the film is performed on a hot plate, or in an oven withinternal air circulation or a vacuum oven. It is preferable toinstantaneously heat the film on a hot plate in order to obtain uniformorientation.

In addition, in order to obtain higher crystallinity, it is preferableto perform rubbing treatment in which a coating film before being heatedis lightly rubbed with cloth or the like. Examples of the cloth to beused for the rubbing treatment include, but not limited to, rayon,cotton, and silk.

An organic semiconductor layer using an orientation film of a benzocompound obtained through those operations has an average thickness of10 to 200 nm, preferably 20 to 100 nm. The term “average thickness” asused herein refers to an average value for film thicknesses measured byusing a surface roughness tester or a step-difference measuringapparatus.

FIG. 4 and FIG. 5 are each an enlarged schematic diagram of a part of afield effect transistor of the present invention. The field effecttransistor of the present invention is constituted of a gate electrode1, a gate insulating layer 2, a source electrode 3, a drain electrode 4,and an organic semiconductor layer 5.

The gate electrode, the source electrode, and the drain electrode arenot particularly limited as long as they are made of conductivematerials. Examples of materials for those electrodes include: platinum,gold, silver, nickel, chromium, copper, iron, tin, antimonial lead,tantalum, indium, aluminum, zinc, and magnesium, and alloys thereof;conductive metal oxides such as an indium tin oxide; and inorganic andorganic semiconductors with conductivities increased by doping or thelike such as a silicon single crystal, polysilicon, amorphous silicon,germanium, graphite, polyacetylene, polyparaphenylene, polythiophene,polypyrrole, polyaniline, polythienylene vinylene, and polyparaphenylenevinylene. Examples of a method of preparing an electrode include asputtering method, an evaporation method, a printing method using asolution or paste, and an ink jet method. Of the electrode materialslisted above, an electrode material having a low electrical resistanceat a contact surface with the semiconductor layer is preferable.

Any gate insulating layer can be used as long as the layer can beuniformly coated with a bicyclo compound solution. However, a gateinsulating layer having a high dielectric constant and a lowconductivity is preferable. Examples of an insulating material for suchan insulating layer include: inorganic oxides and nitrides such assilicon oxide, silicon nitride, aluminum oxide, titanium oxide, andtantalum oxide; and organic polymers such as polyacrylate,polymethacrylate, polyethylene terephthalate, polyimide, polyether, anda siloxane polymer. In addition, of the above insulating materials, aninsulating material having high surface smoothness is preferable.

To improve coating film uniformity of the bicyclo compound solution onthe insulating layer, or to make the orientation of the film of thebenzo compound uniform by heating, only the insulating layer surface canbe modified. Examples of a modification method include: dry treatmentusing ozone, plasma, or hexamethyldisilazane gas; and wet treatmentusing a solution prepared by dissolving tetraalkoxysilane,trichlorosilane, or a surfactant into an organic solvent.

A field effect transistor structure in the present invention may be anyone of a top contact electrode type and a bottom contact electrode type.In addition, the field effect transistor structure in the presentinvention is not limited to a thin film type but may be a stereo type.

Synthesis examples and examples are shown below. However, the presentinvention is not limited to these examples.

SYNTHESIS EXAMPLE 1

Synthesis of Bicyclo Compound

Step (1)

A mixed solution of 3.16 g (39.5 mmol) of 1,3-cyclohexadiene, 10.5 g(34.1 mmol) of trans-1,2-bis(phenylsulfonyl)ethylene, and 200 ml oftoluene was refluxed for 7 hours. Then, the mixed solution was cooledand concentrated under reduced pressure to yield a reaction mixture. Thereaction crude product was recrystallized (chloroform/hexane) to yield5,6-bis(phenylsulfonyl)-bicyclo[2,2,2]octa-2-ene (13.8 g, 35.6 mmol, 90%yield).

Step (2)

A reaction system of a mixed solution of 7.76 g (20 mmol) of theresultant 5,6-bis(phenylsulfonyl)-bicyclo[2,2,2]octa-2-ene and 50 ml ofanhydrous tetrahydrofuran was replaced with nitrogen. Then, 2.425 ml (22mmol) of ethyl isocyanoacetate were added to the mixed solution, and thewhole was cooled to 0° C. Potassium tert-butoxide (50 ml/l M THFsolution) was dropped into the mixture in 2 hours, and the whole wasstirred at room temperature for 3 hours. After the completion of thereaction, diluted hydrochloric acid was added to the reaction mixture.Then, the reaction mixture was washed with a saturated aqueous solutionof sodium hydrogen carbonate, distilled water, and a saturated saltsolution in this order, and was dried with anhydrous sodium sulfate. Thedried product was purified by means of silica gel column chromatography(chloroform) to yieldethyl-4,7-dihydro-4,7-ethano-2H-isoindole-1-carboxylate (3.5 g, 16 mmol,80% yield).

Step (3)

Under an argon atmosphere, a mixed solution of 0.42 g (1.92 mmol) of theresultant ethyl-4,7-dihydro-4,7-ethano-2H-isoindole-1-carboxylate and 50ml of anhydrous THF was cooled to 0° C. Then, 0.228 g (6 mmol) oflithium aluminum hydride powder was added to the mixed solution, and thewhole was stirred for 2 hours. After that, THF was removed, and then theremainder was extracted with chloroform, washed with a saturated aqueoussolution of sodium hydrogen carbonate, distilled water, and a saturatedsalt solution in this order, and dried with anhydrous sodium sulfate.The reaction solution was filtered, replaced with argon, and shaded.Then, 10 mg of p-toluenesulfonic acid were added to the reactionsolution, and the whole was stirred for 12 hours at room temperature.Furthermore, 0.11 g of p-chloranil was added to the mixture, and thewhole was stirred for 12 hours at room temperature. The resultant waswashed with a saturated aqueous solution of sodium hydrogen carbonate,distilled water, and a saturated salt solution in this order, and driedwith anhydrous sodium sulfate. After the concentration of the solution,the concentrated product was subjected to alumina column chromatography(chloroform) and recrystallized (chloroform/methanol) to yield ametal-free bicyclo compound (bicycloporphyrin) represented by thefollowing structural formula (3) (0.060 g, 0.097 mmol, 20% yield).

Step (4)

A solution of 0.02 g (0.032 mmol) of bicycloporphyrin and 0.019 g (0.1mmol) of copper (II) acetate monohydrate in a mixture of 30 ml ofchloroform and 3 ml of methanol was stirred at room temperature for 3hours. The reaction solution was washed with distilled water and asaturated salt solution, and was then dried with anhydrous sodiumsulfate. After the concentration of the solution, the concentratedproduct was recrystallized with chloroform/methanol to yield a bicyclocompound (bicycloporphyrin copper complex) represented by the followingstructural formula (4) (0.022 g, 100% yield).

EXAMPLE 1

FIG. 4 shows the structure of a bottom gate type field effect transistorin this example.

First, a highly doped N-type silicon substrate was provided as the gateelectrode 1. A silicon oxide film of 5,000 Å in thickness obtained bythermal oxidation of the silicon substrate surface layer was provided asthe insulating layer 2. Chromium and gold were deposited from the vaporin this order onto the insulating layer 2 to form the source electrode 3and the drain electrode 4 by means of an ordinary photolithographytechnique. Subsequently, the substrate surface was treated with ozone.Then, a coating film made from a 1 wt % chloroform solution of thebicyclo compound synthesized in Synthesis Example 1 was formed on thesubstrate by means of a spin coating method. Furthermore, the substratewas heated at 220° C. to) form the organic semiconductor layer 5composed of a benzo compound represented by the following structuralformula (5). The organic semiconductor layer had an average thickness of50 nm.

A field effect transistor having a channel length L of 50 μm and achannel width W of 10 mm was prepared according to the above procedure.The V_(d)-I_(d) and V_(g)-I_(d) curves of the prepared transistor weremeasured by using a Parameter Analyzer 4156C (trade name) manufacturedby Agilent, to thereby provide results shown in FIG. 3.

A mobility μ (cm²/Vs) was calculated from the following equation (1).I _(d)=μ(C _(i) W/2L)×(V _(g) −V _(th))²  (Eq. 1)

In the equation, C_(i) denotes a capacitance per unit area (F/cm²) of agate insulating film, and W and L denote the channel width (mm) and the,channel length (μm) described in this example, respectively. Inaddition, I_(d), V_(g), and V_(th) denote a drain current (A), a gatevoltage (V), and a threshold voltage (V), respectively.

Table 1 shows the results. Furthermore, the prepared transistorsubstrate was subjected to CuKα X-ray diffraction under the aboveconditions. FIG. 1 shows the results.

Furthermore, a benzo compound was prepared under the above conditions ona quartz substrate and subjected to CuKα X-ray diffraction as above.FIG. 2 shows the results.

EXAMPLE 2

Operations similar to those of Example 1 were performed except that thechannel length L and the channel width W were changed to 50 μm and 2 mm,respectively. Table 1 shows the results. In addition, CuKα X-raydiffraction was performed under the conditions of Example 1 to providesimilar diffraction.

EXAMPLE 3

Operations similar to those of Example 1 were performed except that thetransistor structure was changed to a top electrode type field effecttransistor as described below.

FIG. 5 shows the structure of a top electrode type field effecttransistor.

First, a highly doped N-type silicon substrate was provided as the gateelectrode 1. A silicon oxide film of 5,000 Å in thickness obtained bythermal oxidation of the silicon substrate surface layer was provided asthe gate insulating layer 2. Subsequently, the substrate surface wastreated with ozone. Then, a coating film made from a 1 wt % chloroformsolution of the bicyclo compound synthesized in Synthesis Example 1 wasformed on the substrate by means of a spin coating method. Furthermore,the substrate was heated at 220° C. to form the organic semiconductorlayer 5 composed of a benzo compound. The organic semiconductor layer onthe substrate had an average thickness of 50 nm. Chromium and gold weredeposited from the vapor in this order onto the organic semiconductorlayer 5 to form the source electrode 3 and the drain electrode 4 with achannel length L of 50 μm and a channel width W of 10 mm by means of anordinary photolithography technique. Table 1 shows the results. Inaddition, CuKα X-ray diffraction was performed under the conditions ofExample 1 to provide similar diffraction.

EXAMPLE 4

Operations similar to those of Example 3 were performed except that thechannel length L and the channel width W were changed to 50 μm and 2 mm,respectively. Table 1 shows the results. In addition, CuKα X-raydiffraction was performed under the conditions of Example 1 to providesimilar diffraction. TABLE 1 Mobility ON/OFF W(mm)/L(μm) (cm²/Vs) ratioExample 1 10/50 0.09 1.5 × 10⁴ Example 2  2/50 0.09 1.3 × 10⁴ Example 310/50 0.09 1.7 × 10⁴ Example 4  2/50 0.10 1.6 × 10⁴

The field effect transistor of the present invention can be used forvarious devices in the fields of organic electronics and optoelectronicsbecause of its high field effect mobility. In addition, with the methodof manufacturing a field effect transistor of the present invention, anorganic semiconductor layer can be formed much simply than aconventional method, and the method can be used for manufacturing afield effect transistor exhibiting a high field effect mobility.

This application claims priority from Japanese Patent Application No.2003-305487 filed on Aug. 28, 2003, which is hereby incorporated byreference herein.

1. A field effect transistor comprising an organic semiconductor layer,wherein the organic semiconductor layer contains at least a tetrabenzocopper porphyrin crystal and has peaks at two or more of Bragg angles(2θ) in CuKα X-ray diffraction of 8.40°±0.20°, 10.20°±0.20°,11.8°±0.20°, and 16.9°±0.20°.
 2. The field effect transistor accordingto claim 1, wherein the tetrabenzo copper porphyrin crystal comprises acompound represented by the following general formula (1).

(Wherein R₂'s each independently represent at least one kind selectedfrom the group consisting of a hydrogen atom, a halogen atom, a hydroxylgroup, and an alkyl group, oxyalkyl group, thioalkyl group, oralkylester group having 1 to 12 carbon atoms, and R₃'s represent atleast one kind selected from the group consisting of a hydrogen atom andan aryl group.)
 3. The field effect transistor according to claim 1 or2, wherein the tetrabenzo copper porphyrin crystal is obtained byheating a compound represented by the following general formula (2).

(Wherein R₁'s and R₂'s each independently represent at least one kindselected from the group consisting of a hydrogen atom, a halogen atom, ahydroxyl group, and an alkyl group, oxyalkyl group, thioalkyl group, oralkylester group having 1 to 12 carbon atoms, and R₃'s represent atleast one kind selected from the group consisting of a hydrogen atom andan aryl group.)
 4. A method of manufacturing a field effect transistorhaving an organic semiconductor layer, comprising the step of formingthe organic semiconductor layer containing at least a tetrabenzo copperporphyrin crystal and having peaks at two or more of Bragg angles (2θ)in CuKα X-ray diffraction of 8.4°±0.2°, 10.20°±0.20°, 11.80°±0.2°, and16.9°±0.2°, wherein the step of forming the organic semiconductor layeris performed by heating a thin film comprising a compound represented bythe following general formula (2) to produce the tetrabenzo copperporphyrin crystal.

(Wherein R₁'s and R₂'s each independently represent at least one kindselected from the group consisting of a hydrogen atom, a halogen atom, ahydroxyl group, and an alkyl group, oxyalkyl group, thioalkyl group, oralkylester group having 1 to 12 carbon atoms, and R₃'s represent atleast one kind selected from the group consisting of a hydrogen atom andan aryl group.)